Esterlike condensation products and a process of preparing them



Patented May 19, 1942 ESTERLIKE CONDENSA'IION PRODUCTS AND A PROCESS OF PREPARING THEM Johann Rosenbach, Wiesbaden, and Gerhard Balle, Frankfort-on-the-Main, Germany, as-

signors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application May 3, 1939, Serial No. 271,512. In Germany May 6, 1938 11 Claims. (Cl. 260-484) --CON OCON X1 one of the groups CON/ OCON

R: stands for hydrogen or alkyl and Hal for a halogen atom, to react with a salt of a carboxylic acid.

Such halogen-methyl compounds suitable for use in the present process are, for instance, halogen-methyl ethers of monoor polyhydric alcohols, such as dodecanols, octadecanols, oleyl alcohol, montan alcohols. resin alcohols and the hydrogenation products thereof, octadecane-diol, dichloro-octadecane diol, octadecylmonoglycol ether, para-butylphenyl-butanol, octadecylphenyldiglycol ether, naphthene alcohols. The corresponding halogen-methyl compounds may, for instance, be produced in the manner indicated in British Patent No. 394,196.

There are further suitable halogen-methyl compounds of monoor polyvalent mercaptans, such as dodecyl mercaptan, octadecyl mercaptan; these compounds may be prepared in a manner analogous to that indicated for the above-mentioned halogen-methyl ethers.

Furthermore N-halogenmethyl compounds of carboxylic acid amides or carbamic acid esters, such as: lauric acid amide, stearic acid amide, oleic acid amide, aceto-N-octadecyl amide, bu-

tyricacid-N-dodecyl amide, stearic acid methyl amide, montanic acid amide, resinic acid amide,

' the amides of carboxylic acids having at least 12 carbon atoms obtainable by oxidizing paraflin or by similar processes, furthermore, dichlorostearic acid amide, ricinoleic acid methylamide, iso-octylphenoxy-acetic acid amide, iso-dodecyl-cyclohexyl-hydroxy-acetic acid amide, tributylphenylacetic acid-N-butylamide, para-butylphenyl-butyric acid amide, carbamic acid dodecyl ester, N-methylcarbamic acid octadecyl ester, carbamic acid-iso-dodecylphenyl ester, N-methyl-carbamic acid-iso-dodecylcyclohexylglycol ester. The corresponding halogen-methyl compounds may, for instance, be produced in the manner indicated in French Patents Nos. 818,438 and 819,945.

Carboxylic acids the salts of which may be caused to react with the halogen-methyl compounds according to the process of the present invention are, for instance: formic acid, acetic acid, butyric acid, lauric acid, stearic acid, oleic acid, montanic acid, resinic acid, chloracetic acid, dichloracetic acid, glycollic acid, dimethylaminoacetic acid, beta-chloropropionic acid, alphabromo-lauric acid, alpha-dimethylamino-stearic acid, ricinoleic acid, butoxy-acetic acid, phenoxyacetic acid, alkylphenoxyacetic acid, phenylacetic acid, butylphenylbutyric acid and also polyvalent aliphatic carboxylic acids such as succinic acid, adipic acid, diglycollic acid and aromatic carboxylic acids, for instance, benzoic acid, chlorobenzoic acid, phthalic acid.

The reaction to form the ester-like constituted reaction products is preferably performed by heating the halogen-methyl compound in an organic solvent together with a salt of a carboxylic acid at a temperature between about C. and

' about C., isolating by filtration the inorganic salt which has separated and removing the solvent by distillation. The ester-like condensation products thus obtained are generally solids of low melting point which are insoluble in water and, in most cases, easily soluble in organic solvents. They may be used for rendering waterrepellent natural or artificial fibrous materials of vegetable or animal origin. It is necessary, in this process, to subject the impregnated textile material subsequently to a treatment between 80 C. and C., the degree of the temperature depending on the kind of the product used. It

, is in some cases of advantage to use simultaneously a feeble acid, such as lactic acid, tartaric acid or glycollic acid.

The following examples serve to illustrate the salicylic acid, naphthoic acid,

invention, but they are not intended to limit it thereto; the parts are by weight:

1. 30 parts of anhydrous potassium acetate are added to a solution of 77 parts of commercial octadecylchloromethyl ether in 400 parts of methylene chloride and the whole is heated to boiling, for hours, while stirring. The potassium chloride formed is filtered and the solvent is distilled. The ester obtained is purified by recrystallizing it from methanol. It is a colourless mass having a low melting point.

2. A mixture of '77 parts of commercial octadecylchloromethyl ether, 500 parts of methylene chloride and 30 parts of sodium chloracetate is kept boiling, for hours, while stirring. After cooling, the sodium chloride formed is filtered and the methylene chloride is distilled, under reduced pressure, at a temperature of 30 C. to 40 C. The product corresponds with the formula: v

C1BH37.O.CH2O.CO.CH2C1 It is a colourless body having a low melting point.

3. 50 parts of dry potassium acetate are added to a solution of 106 parts of stearic acid chloromethylamide in 800 parts of carbon tetrachloride and the whole is heated to boiling. for 8 hou s. After cooling, the undissolved matter is filtered with suction and the filtrate is evaporated, under reduced pressure, at a temperature of 50 C. The residue is recrystallized from methanol and melts then at 58 C. to 62 C. By redissolving from, for instance, methylene chloride and eliminating the most difiicultly soluble parts by filtration a product is obtained melting at about 83 C. to about 85 C.

4. A mixture of 70 parts of N-chloromethylcarbamic acid octadecyl ester, 500 parts of methylene chloride and parts of sodium chloracetate is heated to boiling, for 12 hours, while stirring under reflux. -After cooling, the undissolved matter is filtered off and the filtrate is evaporated, under reduced pressure, at a temperature of 40 C. to 50 C. The compound obtained corresponds with the formula:

CisH37.O.CO.NH.CI-I2.O.CO.CH2C1 It is a colourless low-melting body.

5. 16 parts of potassium benzoate are added to a solution of parts of N-chloromethyl-carbamic acid paraoctylphenyl ester in 250 parts of carbon tetrachloride and the whole is heated to boiling, for 10 hours, while stirring. The potassium chloride formed is then filtered and the filtrate is evaporated, under reduced pressure, at 30 C.

6. A mixture of 25 parts of sodium dimethylaminoacetate, 64 parts of octadecyl-chloromethyl ether and 300 parts of benzene is heated to boiling for 2 hours, the sodium chloride which separates is filtered and the benzene is distilled. un-' der reduced pressure, at a temperature of 30 C. to C. In order to purify the ester obtained the residue is treated, for some time, with cold acetone and the matter insoluble in acetone is then filtered with suction. After evaporating the filtrate the ester of the formula:

CE; CiaHa7.0.CHz.O.C O.CH:.N

is obtained in the form of a soft, brownish mass which on cautiously heating dissolves in dilute acetic acid to a clear solution.

'7. 60 parts of sodium chloracetate are added to a solution of parts of dodecyl-chloromethylsulfide in 1000. parts of benzene and the whole is heated to boiling for 7 hours while stirring. The sodium chloride formed is separated by filtering and the solvent is distilled under reduced pressure.

8. A mixture of 200 parts of octadecyl-chloromethyl ether, parts of potassium phonoxyacetate and 400 parts of benzene is heated to boiling for 5 hours while stirring. The potassium chloride formed is thereupon separated by filtering while hot and the filtrate is evaporated under reduced pressure. In order to purify the residue obtained it is recrystallized from alcohol. A colorless solid body is obtained which dissolves in benzene and in carbontetrachloride already in the cold, but in alcohol only in the heat.

9. parts of octadecyl-chloromethyl ether are heated to boiling for 8 hours together with 80 parts of the potassium salt of diglycollic acid and 400 parts of benzene. The undissolved salts are separated by filtering while hot and the crystalline mass, which has separated after cooling the filtrate, is filtered with suction. The product obtained has the following constitution:

CrsHJ1-O.CH2.0.CO.CH:

After recrystallization from alcohol the product melts at 71 C.

10. 73 parts of the potassium salt of phthalic acid are added to a solution of 160 parts of octadecylchloromethyl ether in 300 parts of benzene and the whole is heated to boiling for 5 hours while stirring. The solution is filtered while hot and the filtrate is allowed to cool slowly. The ester formed separates in a crystalline form. After filtering with suction and drying the product melts at 55 C. to 61 C.

11. 29 parts of 1.12-octadecane-diol and 8 parts of para-formaldehyde are treated in about 30 parts of benzene at 10 C. to 15 C. with hydrochloric-acid gas until dissolution in and saturation with hydrochloric acid is attained. The solution is dried with calcium chloride and filtered. The hydrochloric acid in excess is removed by distilling about one-third of the solvent. 24 parts of finely pulverized sodium chloracetate are added to the solution and the whole is heated to boiling. After 4 hours 6 parts of finely pulverized sodium chloracetate are added and the whole is further heated for 3 hours under reflux. The solution is then filtered while hot and the filtrate is finally evaporated under reduced pressure. There are obtained about 52 parts of a yellowish oil which consists for the main part of a compound of the formula 1 .12- (C1.CH2.0.CH20) z.C1aH3a C1 calculated, 14.5 per cent. Cl found, 13.7 per cent.

12. 320 parts of octadecylchloromethyl ether are dissolved in 650 parts of methylene chloride and the whole is heated to boiling together with parts of sodium dichloracetate for 6 hours under reflux. The salts are then filtered with suction and the filtrate is freed from the solvent under reduced pressure. The wax-like residue is the dichloroacetic acid ester of the formula C1aI-T37.O.CH2.O.CO.CHCI:4

I claim: 1. The process of manufacturing ester-like condensation products which comprises heating a chloromethyl ether of the general formula wherein R. stands, for an aliphatic hydrocarbon radical of at least 12 carbon atoms, with an aliphatic carboxylic acid alkali metal salt to a temperature between about 50 C. and about 110 C. in the presence of an organic solvent.

2. The process which comprises heating octadecylchloromethyl ether with potassium acetate to a temperaturebetween about 50 C. and about 110 C. in the presence of an organic solvent.

3. The process which comprises heating octadecylchloromethyl ether with sodium chlrnocmocon:

wherein R. stands for an aliphatic hydrocarbon radical of at least 12 carbon atoms, OCORa stands for the acyl radical of an aliphatic carboxylic acid.

6. The compound of the formula CmHamQCI-IaOCOCI-Ia 7. The compound of the formula Ci8H3'l-O.CH2.0COCH2C1 8. The compound of the formula C1aHa7.0.CHz.OCOCH-z CxsHai.O.CH2.0COCHz 9. The process of manufacturing ester-like condensation products which comprises reacting a compound having the general formula R.X.CH2I-Ia1 wherein R stands for a radical seleete d from the group consisting of aliphatic, aliphatic-cycloaliphatic and araliphatic radicals, X stands for a member of the group consisting of oxygen and sulfur and Hal stands for halogen, .and wherein the radical R contains at least 12 carbon atoms,

with a carboxylic acid metal salt.

10. The process of, manufacturing ester-like condensation products which comprises heating a compound having the general formula wherein R stands for aradical selected from the group consisting of aliphatic, aliphatic-cycloaliphatic and araliphatic radicals, X standsfor a member of the group consisting of oxygen and.

sulfur and Hal stands for halogen, and wherein the radical R contains at least 12 carbon atoms,

with a carboxylic' acid metal salt, to a temperature between about and about C. in the presence of an organic solvent. 11. The compounds of the general formula R.X.CH2OCOR2 wherein R stands for a radical selected from the group consisting of'aliph'atic, aliphatic-cycloaliphatic and araliphatic radicals, X stands for a member selected from the group consisting of oxygen and sulfur and OCORz stands for the acyl radical of a carboxylic acid, and wherein the radical R contains at least 12 carbon atoms.

JOHANN ROSENBACH. GERHARD BALLE. 

